Non-metallocene rare earth complex catalysts, methods for their preparation and use

Abstract

This invention proposes a non-ceramic rare-earth complex catalyst, its preparation method, and its application, belonging to the field of polyolefin catalyst technology. The non-ceramic rare-earth complex catalyst has a complex with the structure shown in Formula 1: Formula 1; wherein, R1-R 29 Selected independently from hydrogen and C 1‑9 Alkyl, C 1‑6 Alkoxy, fluorine, chlorine, bromine, iodine; Y is independently selected from rare earth metals scandium, yttrium, lanthanum, neodymium. In this invention, ligands containing N and P atoms that are directly bonded have a good stabilizing effect on rare earth centers, exhibiting good coordination ability and stability in the synthesis of non-ceramic rare earth complex catalysts. The synthesized NP-type non-ceramic rare earth metal complexes have good thermal stability.

Description

Technical Field

[0001] This invention belongs to the field of polyolefin catalyst technology, and particularly relates to non-locene rare earth complex catalysts, their preparation methods and applications. Background Technology

[0002] Rubber, as an important branch of polymer materials, is an indispensable material for the national economy and daily life. Cis-1,4-polydiene is a promising material to replace natural rubber and some commercial high-performance elastomers; trans-1,4-polydiene and 3,4-(or 1,2-)-polydiene are the main components in tire manufacturing, while the synthesis of polyisoprene is closely related to the development of catalysts.

[0003] In the 1960s, China invented the first rare earth compound capable of catalyzing the polymerization of diolefins. Since then, major rubber companies have developed a series of catalytic systems based on this. The main reason is that rare earth catalytic systems are superior to other metal catalytic systems such as titanium and nickel in terms of catalytic activity and cis-1,4 selectivity for the polymerization of isoprene and butadiene. Moreover, the resulting polyisoprene and polybutadiene rubbers have good comprehensive properties, such as less gel, easy processing, wear resistance, tear resistance, and high raw rubber strength.

[0004] Non-cenyl rare earth metal complexes possess advantages such as relative stability, simple synthesis, and low cost. In recent years, research on non-cenyl rare earth metal complexes has reached or surpassed that of cenyl metal complexes. Studies have shown that ligands containing NPN, PNP, and NSN types as non-cenyl coordination groups have a good stabilizing effect on rare earth metal centers, and these non-cenyl rare earth complexes exhibit high activity and high stereoselectivity in the polymerization of conjugated olefins.

[0005] Ligands with direct N and P atom bonding have shown good coordination ability and stability in the synthesis of non-ceramic rare earth complexes, and some non-ceramic rare earth complexes have shown high polymerization activity and stereoselectivity in the polymerization of conjugated olefins. Summary of the Invention

[0006] This invention develops a method for preparing non-locene rare earth catalysts with a simple synthetic route and low raw material cost by synthesizing novel NP-type ligands and their rare earth complexes, so as to achieve highly active and stereoselective polymerization of conjugated olefins.

[0007] This invention proposes a non-locene rare earth complex catalyst, wherein the non-locene rare earth complex catalyst has a complex with the structure shown in Formula 1:

[0008] Formula 1; Among them, R1-R 29 Selected independently from hydrogen and C 1-9 Alkyl, C1-6 Alkyl groups, fluorine, chlorine, bromine, iodine; Y is independently selected from rare earth metals scandium, yttrium, lanthanum, and neodymium.

[0009] Furthermore, the complex having the structure shown in Formula 1 is: Formula 1-1 Formula 1-2 Equation 1-3.

[0010] This invention also proposes a method for preparing any of the above-mentioned non-rare earth element complex catalysts, comprising the following steps: The compound ligand having the structure shown in Formula 2 is reacted with a complex containing rare earth metal having the structure shown in Formula 3 to obtain a complex having the structure shown in Formula 1. Formula 2; Formula 3; Among them, R1-R 29 Selected independently from hydrogen and C 1-9 Alkyl, C 1-6 Alkyl groups, fluorine, chlorine, bromine, iodine; Y is independently selected from rare earth metals scandium, yttrium, lanthanum, and neodymium.

[0011] Furthermore, at least one of the following conditions must be met: (1) The molar ratio of the rare earth metal-containing complex having the structure shown in Formula 3 to the compound having the structure shown in Formula 2 is 1:1 to 2. (2) The reaction temperature is 0-120℃; the reaction time can be 8-36 hours.

[0012] (3) The reaction is carried out in an organic solvent, which is selected from at least one of alkane or aromatic solvent; preferably, the alkane is n-hexane; and the aromatic is toluene.

[0013] Furthermore, the ligand of the compound having the structure shown in Formula 2 is: Formula 2-1 Equation 2-2 Equation 2-3.

[0014] Furthermore, the compound ligand having the structure shown in Formula 2 is prepared by the following steps: The compound phenylhydrazine hydrochloride having the structure shown in Formula 4 was subjected to a substitution reaction with the compound diphenylphosphine chloride having the structure shown in Formula 5 to obtain the compound phenylhydrazine ligand having the structure shown in Formula 2: Equation 4; Formula 5; Among them, R1-R15 Selected independently from hydrogen and C 1-9 Alkyl, C 1-6 Alkyl groups, fluorine, chlorine, bromine, iodine; Preferably, the molar ratio of the compound phenylhydrazine hydrochloride having the structure shown in Formula 4 and the compound diphenylphosphine chloride having the structure shown in Formula 5 is 1:1 to 3. More preferably, the substitution reaction is carried out in a solvent; the solvent includes at least one of ethers and haloalkanes; More preferably, the ether is methyl tert-butyl ether; and the haloalkane is dichloromethane.

[0015] The present invention also proposes a catalyst system comprising any of the non-locene rare earth complex catalysts described above or the non-locene rare earth complex catalysts prepared by any of the preparation methods described above.

[0016] Furthermore, it also includes a co-catalyst, which is selected from at least one of aluminoxane, alkylaluminum, or borate; Preferably, the aluminoxane includes at least one of methylaluminoxane, ethylaluminoxane, or isobutylaluminoxane; Preferably, the alkylaluminum comprises at least one of trimethylaluminum, triethylaluminum, or triisobutylaluminum; Preferably, the borate includes at least one of triphenylmethyltetra(pentafluorophenyl)boron, tri(pentafluorophenyl)boron, and N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate; More preferably, the molar ratio of rare earth metals in the co-catalyst and the non-metallic rare earth complex catalyst is (1~100):1.

[0017] The present invention also proposes the application of any of the above-described catalyst systems in the catalytic polymerization of conjugated olefins.

[0018] Furthermore, the conjugated olefin is isoprene or butadiene.

[0019] This invention has the following advantages: This invention proposes a series of NP-type non-ceramic rare-earth metal complexes containing both N and P atoms and their corresponding preparation methods. These complexes are then applied to the polymerization of conjugated dienes. Utilizing their different electron-donating, electron-withdrawing, and steric hindrance effects, a series of polymers with varying activities and stereoselectivity are synthesized, ultimately achieving stereocontrollable polymerization. The ligands containing N and P atoms that form direct bonds in this invention have a good stabilizing effect on the rare-earth center, exhibiting good coordination ability and stability in the synthesis of non-ceramic rare-earth metal complex catalysts. The synthesized NP-type non-ceramic rare-earth metal complexes show good thermal stability. Their activity in catalyzing isoprene polymerization can reach as high as 7.53 × 10⁻⁶. 6 g·mol -1(Y) ·h -1 The monomer conversion rate reached over 99%, and the number-average molecular weight of the prepared polyisoprene reached 58.3 × 10⁻⁶. 4 g·mol -1 The molecular weight distribution is narrow (down to 1.56). Its activity in catalyzing butadiene polymerization can reach 2.99 × 10⁻⁶. 6 g·mol -1 (Y) ·h -1 The molecular weight distribution is as low as 1.78, and the selectivity for the cis-1,4-structure can reach 99.1%. This invention has good application prospects in the production of synthetic rubber. Detailed Implementation

[0020] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Unless otherwise specified, the embodiments and features in the embodiments of the present invention can be combined with each other.

[0021] One embodiment of the present invention provides a non-locene rare earth complex catalyst having a complex having the structure shown in Formula 1: Formula 1; in, R1-R 29 Selected independently from hydrogen and C 1-9 Alkyl, C 1-6 Alkyl groups, fluorine, chlorine, bromine, iodine; Y is independently selected from rare earth metals scandium, yttrium, lanthanum, and neodymium.

[0022] In a preferred embodiment of the present invention, the complex having the structure shown in Formula 1 is: Formula 1-1 Formula 1-2 Equation 1-3.

[0023] In a preferred embodiment of the present invention, the complex having the structure shown in Formula 1 is selected from: Y represents the rare earth metals yttrium, lanthanum, and neodymium, R1-R 29 All are hydrogen; or Y represents the rare earth metals yttrium, lanthanum, and neodymium; R4 represents methyl; and R1-R3 and R5-R... 29 All are hydrogen; or Y represents the rare earth metals yttrium, lanthanum, and neodymium; R4 represents fluorine; and R1-R3 and R5-R... 29 Both are hydrogen.

[0024] In another aspect, embodiments of the present invention also provide a method for preparing any of the above-mentioned non-locene rare earth complex catalysts, comprising the following steps: The compound ligand having the structure shown in Formula 2 is reacted with a complex containing rare earth metal having the structure shown in Formula 3 to obtain a complex having the structure shown in Formula 1. Formula 2; Formula 3; in, R1-R 29 Selected independently from hydrogen and C 1-9 Alkyl, C 1-6 Alkyl groups, fluorine, chlorine, bromine, iodine; Y is independently selected from rare earth metals scandium (Sc), yttrium (Y), lanthanum (La), and neodymium (Nd).

[0025] The preparation method of the non-locene rare earth complex catalyst proposed in this invention is simple, uses inexpensive raw materials, and has mild reaction conditions.

[0026] In one embodiment of the present invention, the reaction is carried out under a protective atmosphere. The protective atmosphere includes nitrogen, helium, argon, etc.

[0027] In one embodiment of the present invention, the molar ratio of the rare earth metal-containing complex having the structure shown in Formula 3 to the compound having the structure shown in Formula 2 is 1:1 to 2, preferably 1:1 to 1.5.

[0028] In one embodiment of the present invention, the reaction temperature is 0-120°C, for example, 0°C, 20°C, 25°C, or 40°C. The reaction time is 8-36 hours, preferably 24 hours.

[0029] In one embodiment of the present invention, the reaction is carried out in an organic solvent. The organic solvent is selected from at least one of alkane or aromatic solvents. For example, the alkane is n-hexane; the aromatic is toluene.

[0030] In one embodiment of the present invention, the reaction further includes, after the reaction, drying the solvent under reduced pressure, washing the remaining solid multiple times with a small amount of solvent, and then drying under vacuum to obtain the product. The solvent may be icy n-hexane.

[0031] In a preferred embodiment of the present invention, the compound ligand having the structure shown in Formula 2 is: Formula 2-1 Equation 2-2 Equation 2-3.

[0032] Specifically, in Equation 2-1, R1-R 25 Both are hydrogen.

[0033] Specifically, in formula 2-2, R4 is a methyl group, and R1-R3 and R5-R 25 Both are hydrogen.

[0034] Specifically, in Equation 2-3, R4 is fluorine, and R1-R3 and R5-R 25 Both are hydrogen.

[0035] In one embodiment of the present invention, a compound ligand having the structure shown in Formula 2 is prepared by the following steps. The compound phenylhydrazine hydrochloride having the structure shown in Formula 4 was subjected to a substitution reaction with the compound diphenylphosphine chloride having the structure shown in Formula 5 to obtain the compound phenylhydrazine ligand having the structure shown in Formula 2: Equation 4; Formula 5; Among them, R1-R 15 Selected independently from hydrogen and C 1-9 Alkyl, C 1-6 Alkyl groups, fluorine, chlorine, bromine, and iodine.

[0036] Specifically, the molar ratio of the compound phenylhydrazine hydrochloride having the structure shown in Formula 4 and the compound diphenylphosphine chloride having the structure shown in Formula 5 is 1:1 to 3.

[0037] Specifically, the substitution reaction is carried out under the catalysis of triethylamine (Et3N).

[0038] Specifically, the substitution reaction is carried out in a solvent. More specifically, the solvent includes at least one of ethers and haloalkanes. For example, the ether can be methyl tert-butyl ether (MTBE); the haloalkanes can be dichloromethane, etc.

[0039] Specifically, the substitution reaction lasts for 1-72 hours. Preferably, the reaction lasts for 6-48 hours.

[0040] In a preferred embodiment of the present invention, the compound ligand having the structure shown in Formula 3 is specifically a compound having the structure shown in Formula 3-1: Equation 3-1.

[0041] In one embodiment of the present invention, the preparation method of the complex having the structure shown in Formula 3 is a conventional method. Specifically, the complex having the structure shown in Formula 3 is prepared by the following steps: reacting a rare earth metal halide (YCl3) with a lithium salt corresponding to the structure shown in Formula 3, washing the resulting product, dissolving it in toluene, concentrating and crystallizing it to obtain the complex having the structure shown in Formula 3.

[0042] In another aspect, embodiments of the present invention also provide a catalyst system comprising any of the non-locene rare earth complex catalysts described above.

[0043] Furthermore, it also includes a co-catalyst selected from at least one of aluminoxane, alkylaluminum, or borate.

[0044] Specifically, the aluminum oxane includes at least one of methylaluminoxane (MAO), ethylaluminoxane (EAO), or isobutylaluminoxane (i-BAO).

[0045] Specifically, the alkylaluminum includes trimethylaluminum (AlMe3), triethylaluminum (AlEt3), or triisobutylaluminum (Al... i At least one of Bu3).

[0046] Specifically, the borate includes at least one of triphenylmethyltetra(pentafluorophenyl)boron ([Ph3C][B(C6F5)4]), tri(pentafluorophenyl)boron (B(C6F5)3]), and N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate ([PhNMe2H][B(C6F5)4]).

[0047] In one embodiment of the present invention, the molar ratio of rare earth metal in the co-catalyst and the non-locene rare earth complex catalyst is (1~100):1, for example, it can be 1:1, 2:1, 3:1, 5:1, 7:1, 8:1, 10:1, 20:1, 30:1, 50:1 or 100:1, etc.

[0048] In another aspect, embodiments of the present invention also propose the application of any of the above-mentioned catalyst systems in the polymerization reaction of conjugated olefins.

[0049] In one embodiment of the present invention, the conjugated olefin is isoprene or butadiene.

[0050] In this embodiment of the invention, a catalyst system containing a non-locene rare earth complex catalyst is used to catalyze the polymerization reaction of conjugated olefins such as isoprene or butadiene to generate polyisoprene or polybutadiene, resulting in polymers with controllable microstructure and molecular weight, which have great application prospects.

[0051] The NP-type non-locene rare earth metal complex catalyst proposed in this invention exhibits high catalytic activity when used for the polymerization of isoprene or butadiene.

[0052] In one embodiment of the present invention, the polymerization reaction temperature is 10-100℃.

[0053] In one embodiment of the present invention, the polymerization reaction time is 1-60 min. Preferably, the polymerization reaction time is 1-30 min.

[0054] In this invention, ligands containing N and P atoms that form direct bonds have a good stabilizing effect on rare earth centers, exhibiting good coordination ability and stability in the synthesis of non-ceramic rare earth complexes. The synthesized NP-type non-ceramic rare earth metal complexes have good thermal stability, and their activity in catalyzing isoprene polymerization at 80°C can reach 108.69 × 10⁻⁶. 4 g·mol -1 (Y1) ·h -1 .

[0055] The present invention will now be described in detail with reference to the embodiments.

[0056] The invention will now be described in detail with reference to specific examples.

[0057] Example 1 The NP-type ligand shown in Formula 2-1 was prepared. Phenylan hydrochloride (1.44 g, 10 mmol) was added to 60 mL of methyl tert-butyl ether (MTBE), and the mixture was stirred thoroughly and kept in an ice bath at 0°C. Excess triethylamine (5.05 g, 50 mmol) was added, and the mixture was kept in an ice bath. Diphenylphosphine chloride (4.41 g, 20 mmol) was added dropwise. Half an hour after the addition was complete, the ice bath was removed, and the reaction was carried out at room temperature for 12 hours under a nitrogen atmosphere. After the reaction was complete, the triethylamine salt was removed by filtration, and the filtrate was obtained. Distilled water and the filtrate were mixed in a separatory funnel, shaken, and separated. This operation was repeated three times. Sufficient anhydrous sodium sulfate was added to the washed filtrate for drying. The solid was removed by filtration, and the filtrate was concentrated using a rotary evaporator to remove the solvent. An appropriate amount of anhydrous ethanol and a small amount of dichloromethane were added to the solid, and the solid was dissolved by heating at 60°C. After multiple recrystallizations, orange crystals (2.92 g, yield 61.28%) were obtained.

[0058] The structural verification data is as follows: 1 H NMR (500 MHz, CDCl3) δ 7.46 – 7.41 (m, 8H), 7.36 – 7.32 (m, 4H), 7.29 (t, J = 7.5 Hz, 8H), 6.96 (dd, J = 8.5, 7.2 Hz, 2H), 6.66 (t, J = 7.4Hz, 1H), 6.46 (d, J = 7.9 Hz, 2H), 5.83 (s, 1H). Example 2 Preparation of NP-type ligands as shown in Formula 2-2 3-Methylphenylhydrazine hydrochloride (1.59 g, 10 mmol) was added to 60 mL of methyl tert-butyl ether and stirred thoroughly in an ice bath at 0°C. Excess triethylamine (5.05 g, 50 mmol) was added, and the mixture was kept in an ice bath. Diphenylphosphine chloride (4.41 g, 20 mmol) was added dropwise. Half an hour after the addition was complete, the ice bath was removed, and the reaction was carried out at room temperature for 12 hours under a nitrogen atmosphere. After the reaction was complete, the triethylamine salt was removed by filtration, and the filtrate was obtained. Distilled water and the filtrate were mixed in a separatory funnel, shaken, and separated. This operation was repeated three times. Sufficient anhydrous sodium sulfate was added to the washed filtrate for drying. The sodium sulfate solid was removed by filtration, and the filtrate was concentrated using a rotary evaporator to remove the solvent. An appropriate amount of anhydrous ethanol and a small amount of dichloromethane were added to the solid, and the solid was dissolved by heating at 60°C. After multiple recrystallizations, yellow crystals (1.36 g, yield 27.73%) were obtained.

[0059] The structural verification data is as follows: 1 H NMR (400 MHz, CDCl3): δ7.55-7.07 (m, 21H), 6.77 (t, J = 7.7 Hz, 1H), 6.39 (d, J = 7.4 Hz, 1H), 6.21 (dd, J= 8.1, 2.3 Hz, 1H), 5.74 (s, 1H), 1.96 (s,3H). 31 P NMR (202 MHz, CDCl3) δ69.18. Example 3 The NP-type ligands shown in Formula 2-3 were prepared. 3-Fluorophenylhydrazine hydrochloride (1.62 g, 10 mmol) was added to 60 mL of methyl tert-butyl ether and stirred thoroughly in an ice bath at 0°C. Excess triethylamine (5.05 g, 50 mmol) was added, and the mixture was kept in an ice bath. Diphenylphosphine chloride (4.41 g, 20 mmol) was added dropwise. Half an hour after the addition was complete, the ice bath was removed, and the reaction was carried out at room temperature for 12 hours under a nitrogen atmosphere. After the reaction was complete, the triethylamine salt was removed by filtration, and the filtrate was obtained. Distilled water and the filtrate were mixed in a separatory funnel, shaken, and separated. This operation was repeated three times. Sufficient anhydrous sodium sulfate was added to the washed filtrate for drying. The sodium sulfate solid was removed by filtration, and the filtrate was concentrated using a rotary evaporator to remove the solvent. An appropriate amount of anhydrous ethanol and a small amount of dichloromethane were added to the solid, and the solid was dissolved by heating at 60°C. After multiple recrystallizations, orange crystals (3.05 g, yield 61.68%) were obtained.

[0060] The structural verification data is as follows: 1H NMR (400 MHz, CDCl3) δ 7.49 – 7.42 (m, 8H), 7.40 – 7.27 (m, 12H), 6.87 (td, J = 8.2, 6.5 Hz, 1H), 6.31 (td, J = 8.1, 2.0 Hz, 1H), 6.21 (dd, J = 8.1, 2.1 Hz, 1H), 6.08 (dt, J = 11.4, 2.3 Hz, 1H), 5.99 (s, 1H). Example 4-1 Preparation of NP-type non-locene rare earth metal complexes as shown in Formula 1-1 The ligand is: the NP-type ligand phenylhydrazine hydrochloride ligand obtained in Example 1, which has the formula shown in Formula 2-1; The preparation method of the rare earth yttrium tribenzyl complex Y(CH2C6H4NMe2-o)3 shown in Formula 3-1 can be found in the literature (Half-Sandwich oN,N-Dimethylaminobenzyl Complexes over the Full Size Range of Group 3 and Lanthanide Metals. Synthesis, Structural Characterization, and Catalysis of Phosphine PH Bond Addition to Carbodiimides. Chem. Eur. J.2008, 14, 2167-2179.).

[0061] The reaction was carried out under a nitrogen atmosphere. A phenylhydrazine hydrochloride ligand (1.48 g, 3.1 mmol) and the yttrium tribenzyl complex Y(CH2C6H4NMe2-o)3 (1.47 g, 3.0 mmol) were sequentially placed in a 50 mL Schlenk flask, followed by the addition of 15 mL of toluene. The mixture was stirred at room temperature (25 °C) for 24 hours. The toluene solvent was removed under reduced pressure, and the remaining solid was washed three times with a small amount of ice-cold n-hexane. The solid was then dried under vacuum to constant weight to give a yellow solid (1.83 g, yield 73.25%), designated as complex Y1-1. The structural verification data is as follows: 1 H NMR (600 MHz, CDCl3) δ 7.29 (d, J= 7.6 Hz, 2H), 7.24 – 7.08 (m,18H), 7.07 – 6.99 (m, 9H), 6.95 (t, J = 7.4 Hz, 4H), 3.03 (s, 4H), 2.33 (s, 12H). Example 4-2 Preparation of NP-type non-locene rare earth metal complexes as shown in Formula 1-1 Same as Example 4-1, except that the rare earth yttrillium tribenzyl complex Y(CH2C6H4NMe2-o)3 is replaced with the corresponding lanthanum tribenzyl complex, and the resulting complex is denoted as complex Y1-2.

[0062] Example 4-3 Preparation of NP-type non-locene rare earth metal complexes as shown in Formula 1-1 Same as Example 4-1, except that the rare earth yttribenzyl complex Y(CH2C6H4NMe2-o)3 is replaced with the corresponding neodymium tribenzyl complex, and the resulting complex is denoted as complex Y1-3.

[0063] Example 5-1 Preparation of NP-type non-locene rare earth metal complexes as shown in Formula 1-2 The ligand is: the NP-type ligand 3-methylphenylhydrazine type ligand with Formula 2-2 obtained in Example 2; The preparation method of the rare earth yttrium tribenzyl complex Y(CH2C6H4NMe2-o)3 shown in Formula 3-1 can be found in the literature (Half-Sandwich oN,N-Dimethylaminobenzyl Complexes over the Full Size Range of Group 3 and Lanthanide Metals. Synthesis, Structural Characterization, and Catalysis of Phosphine PH Bond Addition to Carbodiimides. Chem. Eur. J.2008, 14, 2167-2179.).

[0064] The reaction was carried out under a nitrogen atmosphere. 3-Methylphenylhydrazine ligand (1.52 g, 3.1 mmol) and the yttrium tribenzyl complex Y(CH2C6H4NMe2-o)3 (1.47 g, 3.0 mmol) were sequentially placed in a 50 mL Schlenk flask, followed by the addition of 15 mL of toluene. The mixture was stirred at room temperature for 24 hours, and the toluene solvent was removed under reduced pressure. The remaining solid was collected and washed three times with a small amount of ice-cold n-hexane. The solid was then dried under vacuum to constant weight to obtain a creamy-white solid (2.21 g, yield 75.14%), designated as complex Y2-1. The structural verification data is as follows: 1 H NMR (500 MHz, Benzene-d6): δ 7.68 (t, J = 7.7 Hz, 8H), 7.12-7.02(m, 12H), 6.97 (td, J = 7.3, 1.1 Hz, 2H), 6.91 (dd, J = 7.9, 1.2 Hz, 2H), 6.87 (dd, J = 7.7, 1.2 Hz, 2H), 6.82 (td, J = 7.4, 1.2 Hz, 2H), 6.80 (t, J =7.7 Hz, 1H), 6.28 (d, J = 7.3 Hz, 1H), 6.02 (dd, J = 8.0, 2.4 Hz, 1H), 5.91(s, 1H), 2.38 (s, 12H), 1.98 (s, 3H), 1.87-1.57 (m, 4H). Example 5-2 Preparation of NP-type non-locene rare earth metal complexes as shown in Formula 1-2 Same as Example 5-1, except that the rare earth yttrillium tribenzyl complex Y(CH2C6H4NMe2-o)3 is replaced with the corresponding lanthanum tribenzyl complex, and the resulting complex is denoted as complex Y2-2.

[0065] Example 5-3 Preparation of NP-type non-locene rare earth metal complexes as shown in Formula 1-2 Same as Example 5-1, except that the rare earth yttribenzyl complex Y(CH2C6H4NMe2-o)3 is replaced with the corresponding neodymium tribenzyl complex, and the resulting complex is denoted as complex Y2-3.

[0066] Example 6-1 Preparation of NP-type non-locene rare earth metal complexes as shown in Formulas 1-3 The ligand is: the NP-type ligand with formula 2-3 obtained in Example 3, which is a phenylhydrazine hydrochloride ligand; The preparation method of the rare earth yttrium tribenzyl complex Y(CH2C6H4NMe2-o)3 shown in Formula 3-1 can be found in the literature (Half-Sandwich oN,N-Dimethylaminobenzyl Complexes over the Full Size Range of Group 3 and Lanthanide Metals. Synthesis, Structural Characterization, and Catalysis of Phosphine PH Bond Addition to Carbodiimides. Chem. Eur. J.2008, 14, 2167-2179.).

[0067] The reaction was carried out under a nitrogen atmosphere. A 3-fluorophenylhydrazine ligand (1.53 g, 3.1 mmol) and the yttrium tribenzyl complex Y(CH2C6H4NMe2-o)3 (1.47 g, 3.0 mmol) were sequentially placed in a 50 mL Schlenk flask, followed by 15 mL of toluene. The mixture was stirred at room temperature for 24 hours, and the toluene solvent was removed under reduced pressure. The remaining solid was collected and washed three times with a small amount of ice-cold n-hexane. The solid was then dried under vacuum to constant weight to give a pale yellow solid (1.81 g, yield 70.91%), designated as complex Y3-1.

[0068] The structural verification data is as follows: 1 H NMR (400 MHz, CDCl3) δ 7.48 – 7.40 (m, 8H), 7.38 – 7.27 (m, 12H),7.16 (t, J = 6.8 Hz, 4H), 7.04 (d, J = 8.1 Hz, 2H), 6.95 (t, J = 7.3 Hz, 2H), 6.87(q, J = 7.7 Hz, 1H), 6.31 (t, J = 8.3 Hz, 1H), 6.20 (dd, J = 8.3, 2.1 Hz, 1H), 6.06(dt, J = 11.4, 2.4 Hz, 1H), 2.70 (s, 12H), 2.33 (s, 4H). Example 6-2 Preparation of NP-type non-locene rare earth metal complexes as shown in Formulas 1-3 Same as Example 6-1, except that the rare earth yttrillium tribenzyl complex Y(CH2C6H4NMe2-o)3 is replaced with the corresponding lanthanum tribenzyl complex, and the resulting complex is denoted as complex Y3-2.

[0069] Example 6-3 Preparation of NP-type non-locene rare earth metal complexes as shown in Formulas 1-3 Same as Example 6-1, except that the rare earth yttribenzyl complex Y(CH2C6H4NMe2-o)3 is replaced with the corresponding neodymium tribenzyl complex, and the resulting complex is denoted as complex Y3-3.

[0070] Experimental Example 1 The reaction of isoprene polymerization catalyzed by complex Y1-1 Under a nitrogen atmosphere, 3 mL of toluene solution containing catalyst Y1-1 (10 μmol), 1000 μL of isoprene, and 50 μmol of Al were added. i Bu3 and 10 μmol of [Ph3C][B(C6F5)4] were added sequentially to a 25 mL round-bottom flask, at which point the Al / Y (molar ratio) was 5:1. The polymerization temperature was 20℃, and after reacting for 3 minutes, the reaction was terminated with an ethanol solution acidified with 1.0 wt% 2,6-di-tert-butyl-4-methylphenol hydrochloric acid to obtain the polymer. The polymer was washed several times with ethanol, dried under vacuum to constant weight, and weighed.

[0071] It should be noted that in all the experimental examples of this invention, Al / Y (molar ratio) is the molar ratio of aluminum in the co-catalyst to the rare earth metal Y contained in Formula 2 or Formula 3.

[0072] The molecular weight and molecular weight distribution of the polymers obtained by conjugated olefin polymerization were determined using conventional room-temperature GPC methods. The polymerization activity of the polymer is calculated using the following formula: Polymer activity = polymer mass / (catalyst dosage * polymerization time).

[0073] The obtained polymerization activity was 136.20 × 10⁻⁶. 4 g·mol -1 (Y1) ·h -1 The polymer molecular weight Mn = 14.7 × 10⁻⁶ 4 g·mol -1 PDI = 1.97.

[0074] Experimental Example 2 The reaction of isoprene polymerization catalyzed by complex Y2-1 Under a nitrogen atmosphere, 3 mL of toluene solution containing catalyst Y2-1 (10 μmol), 1000 μL of isoprene, and 50 μmol of Al were added. i Bu3 and 10 μmol of [Ph3C][B(C6F5)4] were added sequentially to a 25 mL round-bottom flask, at which point the Al / Y (molar ratio) was 5:1. The polymerization temperature was 30℃, and after reacting for 3 minutes, the reaction was terminated with an ethanol solution acidified with 2,6-di-tert-butyl-4-methylphenol BHT (1.0 wt%) hydrochloric acid to obtain the polymer. The polymer was washed several times with ethanol, dried under vacuum to constant weight, and weighed.

[0075] The polymerization activity is 106.10 × 10⁻⁶. 4 g·mol -1 (Y2) ·h -1 The polymer molecular weight Mn = 56.2 × 10⁻⁶ 4 g·mol -1 PDI = 2.49.

[0076] Experimental Example 3 The reaction of isoprene polymerization catalyzed by complex Y3-1 Under a nitrogen atmosphere, 3 mL of toluene solution containing catalyst Y3-1 (10 μmol), 1000 μL of isoprene, and 50 μmol of Al were added. i Bu3 and 10 μmol of [Ph3C][B(C6F5)4] were added sequentially to a 25 mL round-bottom flask, at which point the Al / Y (molar ratio) was 5:1. The polymerization temperature was 20℃, and after reacting for 2 minutes, the reaction was terminated with an ethanol solution acidified with 2,6-di-tert-butyl-4-methylphenol BHT (1.0 wt%) hydrochloric acid to obtain the polymer. The polymer was washed several times with ethanol, dried under vacuum to constant weight, and weighed.

[0077] The polymerization activity is 204.3 × 10⁻⁶. 4 g·mol -1 (Y3) ·h -1 The polymer molecular weight Mn = 16.6 × 10⁻⁶ 4 g·mol -1 PDI = 2.62.

[0078] Experimental Example 4-13 Similar to Experiment 1, the differences lie in the complex, reaction time, and reaction temperature, as detailed in Table 1.

[0079] Table 1 Test Example 14 Under a nitrogen atmosphere, 2 mL of a chlorobenzene solution containing catalyst Y2-2 (10 μmol), 1000 μL of isoprene, and 50 μmol of Al were added. i Bu3 and 10 μmol of [Ph3C][B(C6F5)4] were added sequentially to a 25 mL round-bottom flask, at which point the Al / Y (molar ratio) was 5:1. The polymerization temperature was 20℃, and after reacting for 2 minutes, the reaction was terminated with an ethanol solution acidified with BHT (1.0 wt%) hydrochloric acid to obtain the polymer. The polymer was washed several times with ethanol, vacuum dried to constant weight, and weighed.

[0080] The polymerization activity is 107.67 × 10⁻⁶. 4 g·mol -1 (Y2) ·h -1 The polymer molecular weight Mn = 67.8 × 10⁻⁶ 4 g·mol -1 PDI = 1.68.

[0081] Experimental Examples 15-19 Similar to Experiment 14, the difference lies in the complex and the aluminum-yttrium ratio, as detailed in Table 2.

[0082] Table 2 Test Example 20 The reaction of butadiene polymerization catalyzed by complex Y3-1 and co-catalyst Under a nitrogen atmosphere, 2 mL of chlorobenzene solution containing catalyst Y3-1 (10 μmol), 500 μL of butadiene, and 30 μmol of Al were added. i Bu3 and 10 μmol of [Ph3C][B(C6F5)4] were added sequentially to a 25 mL round-bottom flask, at which point the Al / Y (molar ratio) was 3:1. The polymerization temperature was 20℃, and after 5 minutes of reaction, the reaction was terminated with an ethanol solution acidified with BHT (1.0 wt%) hydrochloric acid to obtain the polymer. The polymer was washed several times with ethanol, vacuum dried to constant weight, and weighed.

[0083] The polymerization activity is 165.3 × 10⁻⁶. 4 g·mol -1 (Y2) ·h -1 The polymer molecular weight Mn = 18.07 × 10⁻⁶ 4 g·mol -1 PDI = 1.91, cis structure content 98.6%.

[0084] Experimental Examples 21-25 Similar to Experimental Example 20, the difference lies in the complex and reaction temperature, as detailed in Table 3.

[0085] Table 3 Experimental Examples 26-28 Similar to Experiment 20, the difference lies in the aluminum-yttrium ratio, as detailed in Table 4.

[0086] Table 4 The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A non-ceramic rare earth complex catalyst, characterized in that, The non-rare earth-ceramic complex catalyst has a complex with the structure shown in Formula 1: Formula 1; Among them, R1-R 29 Selected independently from hydrogen and C 1-9 Alkyl, C 1-6 Alkyl groups, fluorine, chlorine, bromine, iodine; Y is independently selected from rare earth metals scandium, yttrium, lanthanum, and neodymium.

2. The non-ceramic rare earth complex catalyst according to claim 1, characterized in that, The complex having the structure shown in Formula 1 is: Formula 1-1 Formula 1-2 Equation 1-3.

3. The method for preparing the non-locene rare earth complex catalyst according to claim 1 or 2, characterized in that, Includes the following steps: The compound ligand having the structure shown in Formula 2 is reacted with a complex containing rare earth metal having the structure shown in Formula 3 to obtain a complex having the structure shown in Formula 1. Formula 2; Formula 3; Among them, R1-R 29 Selected independently from hydrogen and C 1-9 Alkyl, C 1-6 Alkyl groups, fluorine, chlorine, bromine, iodine; Y is independently selected from rare earth metals scandium, yttrium, lanthanum, and neodymium.

4. The preparation method according to claim 3, characterized in that, At least one of the following conditions must be met: (1) The molar ratio of the rare earth metal-containing complex having the structure shown in Formula 3 to the compound having the structure shown in Formula 2 is 1:1 to 2. (2) The reaction temperature is 0-120℃; the reaction time can be 8-36 hours. (3) The reaction is carried out in an organic solvent, which is selected from at least one of alkane or aromatic solvent; preferably, the alkane is n-hexane; and the aromatic is toluene.

5. The preparation method according to claim 3, characterized in that, The ligands of compounds having the structure shown in Formula 2 are: Formula 2-1 Equation 2-2 Equation 2-3.

6. The preparation method according to claim 5, characterized in that, Compound ligands having the structure shown in Formula 2 are prepared by the following steps: The compound phenylhydrazine hydrochloride having the structure shown in Formula 4 was subjected to a substitution reaction with the compound diphenylphosphine chloride having the structure shown in Formula 5 to obtain the compound phenylhydrazine ligand having the structure shown in Formula 2: Equation 4; Formula 5; Among them, R1-R 15 Selected independently from hydrogen and C 1-9 Alkyl, C 1-6 Alkyl groups, fluorine, chlorine, bromine, iodine; Preferably, the molar ratio of the compound phenylhydrazine hydrochloride having the structure shown in Formula 4 and the compound diphenylphosphine chloride having the structure shown in Formula 5 is 1:1 to 3. More preferably, the substitution reaction is carried out in a solvent; the solvent includes at least one of ethers and haloalkanes; More preferably, the ether is methyl tert-butyl ether; and the haloalkane is dichloromethane.

7. A catalyst system comprising the non-ceramic rare earth complex catalyst according to any one of claims 1 or 2, or the non-ceramic rare earth complex catalyst prepared by the preparation method according to any one of claims 3 to 6.

8. The catalyst system according to claim 7, characterized in that, It also includes a co-catalyst, which is selected from at least one of aluminoxane, alkylaluminum or borates; Preferably, the aluminoxane includes at least one of methylaluminoxane, ethylaluminoxane, or isobutylaluminoxane; Preferably, the alkylaluminum comprises at least one of trimethylaluminum, triethylaluminum, or triisobutylaluminum; Preferably, the borate includes at least one of triphenylmethyltetra(pentafluorophenyl)boron, tri(pentafluorophenyl)boron, and N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate; More preferably, the molar ratio of rare earth metals in the co-catalyst and the non-metallic rare earth complex catalyst is (1~100):

1.

9. The application of the catalyst system according to claim 8 in the polymerization reaction of conjugated olefins.

10. The catalyst system according to claim 9, characterized in that, The conjugated olefin is isoprene or butadiene.

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